Robust Interface Bonding with B-staged Thermoplastic Polyimide Adhesive

ABSTRACT

Thermoplastic Polyimide (TPI) polymer adhesive coated laminating film in which the TPI coating is under cured or B-staged as well as the process for preparing the film is disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based on the disclosure of Provisional ApplicationSer. No. 61/742,857 filed Aug. 21, 2012, by the same inventor, which ishereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to thermoplastic adhesives and more particularlyto thermoplastic-polyimide (TPI) adhesive lamination films and coatings.

2. Description of the Prior Art

Thermoset adhesives are the dominant bonding technology in mostelectronic applications, generally because they are relativelyinexpensive and easy-to-use. They become very strong through polymercross-linking, usually at elevated temperatures. The resultant bondlineis generally quite brittle. Thermoset adhesives in electronics includeepoxy, acrylic and silicone.

Thermoplastic adhesives are used in applications where a ductilebondline is required. Their polymer chains are very stable, and do notrequire cross-linking Therefore, the resultant bondline has ductility.It will not crack under stress and strain.

Polyimide polymer provides the ultimate in thermal, chemical andstructural durability as opposed to lower temperature thermoplasticpolymers such as, for example, polyethylene, polypropylene, polyester,and polyamide. Most polyimide polymers are made through a condensationreaction within the polymer chain, where a water molecule is eliminatedduring the closure of a carbon ring. Carbon rings within the aromaticpolymer chain are the basis for polyimide polymer stability. Theprecursor polymer is polyamic acid.

Thermoplastic-polyimide (TPI) adhesive provides an exceptional bondlinefor demanding electronic packaging applications, since it is verydurable even at minimal thicknesses. This is especially critical wheretwo different layers with dissimilar Coefficients-of-Thermal-Expansion(CTE) are bonded together and undergo repeated thermal cycles. This is aleading cause of failure in many structures, electronic and otherwise.The ability of TPI adhesive to be ductile and strong make it ideal forthermal-interface bondlines where the need to withstand CTE inducedstress as well as a minimal thickness to maximize thermal transferbetween metal layers, such as between a heat generating device and aheat sink, is required.

TPI adhesive laminate films are known in the prior art and arecommercially available from, for example, DuPont Corporation, WilmingtonDel., under the trade names Pyralux® AP and Kapton® KJ and LJ films;these films are solvent-cast, as is this invention. In addition, TPIadhesive films can be extruded from SABIC's (Riyadh, Saudi Arabia)Ultem® and Extern® resins and DuPont's Aurum® resin. In all of those, asbest known to the applicant, the TPI adhesive is in a fully cured state,i.e., the precursor polymer has been substantially converted to TPI andthe process solvents have been evaporated. Use of these requiresrelatively high temperatures and pressures. In contrast, the under curedor B-staged films and coatings of the present invention can be employedand used in manufacturing operations at moderate conditions approachingthose of conventional thermoset systems. This is accomplished byengineering the drying and curing level of the thermoplastic-polyimideadhesive layer of the film in a way that facilitates handling and use ofthe product. Partially curing the TPI adhesive allows laminationprocessing at much lower temperatures and pressures than a fully curedTPI adhesive layer.

Under curing, or B-staging, thermoplastic-polyimide adhesive allowsbondline processing at much lower temperatures and pressures thanconventional fully cured TPI coatings: the reduction in temperature canbe as much as 80° C. or more; the reduction in pressure can be as muchas 95-99%. The B-staging process for these solvent-cast TPI systems ismuch different than conventional thermoset adhesive systems such as thehigh-solids epoxy and silicones.

TPI polymers in their precursor polyamic-acid (PAA) liquid form are arelatively low-solids solution (<20%) in a strong solvent, such as NMP,DMAc or DMF. NMP or n-pyrol is generally preferred as it is lesshazardous than other equivalent solvents, and when volatilized,evacuates bondlines quickly and smoothly, without blistering. The PAAliquid solution is applied as a thin layer to a substrate, by any of avariety of conventional coating methods. Heat is applied to the coatingthrough a conventional coating oven with hot air, which evaporates offthe solvent at a controlled rate and can start the conversion of the PAAto polyimide (PI). In this invention, only enough heat, hot air, is usedto evaporate a controlled amount of solvent and only a minor conversion,if any, of PAA polymer to PI polymer occurs. Leaving residual solvent inthe B-staged coating dramatically increases the flow of polymer when thecoating is reheated during the lamination process. This is critical inadhesive bondlines where micro-irregular surfaces are being mated.Practically all non-mirror surfaces are very irregular on a micro-level.In addition, the PAA polymer has hydroxyl groups which facilitateadhesion of the polymer to adjacent surfaces. As shown in FIG. 1 below,the schematic shows the condensation reaction of PAA polymer, made fromPMDA/ODA monomers, to generic “Kapton” PI polymer.

It is important to delineate the concept of traditional curing of PAApolymer coatings to PI, as our invention represents a significantdeparture. In prior art, PAA coatings are exposed to very high heatduring the coating process, removing all the solvent and converting muchor all of the PAA to PI. This process removes practically all of thepolymer flow and reactivity characteristics, so such a TPI laminationwould require extremely high temperatures and pressures. Traditionallamination generally requires a very high-temperature platen press orvacuum autoclave. A totally cured TPI adhesive would need to be meltedto provide bonding to adjacent surfaces; this would generally occur at320-350° C. In addition, the fully cured TPI would require immensepressure applied during melting to flow the extremely viscous polymerinto the adjacent surface to ensure adhesion.

The representative process conditions for coating and laminating for arepresentative TPI adhesive polymer are shown in FIG. 2 below, for botha prior art state and the B-staged state of the invention. Other TPIpolymers could have different absolute temperatures and pressures forprocessing, but the relative differences between traditional cure andB-staged states would be about the same as the example shown. Coatingand employment of the film in laminating procedures are performedsequentially, with different processes and generally at differentlocations.

SUMMARY OF THE INVENTION

The invention may be summarized as a Thermoplastic Polyimide (TPI)polymer adhesive coated laminating film and coatings in which the TPIcoating is under-cured or B-staged as well as the process for preparingand using the films and coatings.

The invention provides a number of features and advantages including:

Utilizing the B-stage of a thermoplastic-polyimide (TPI) adhesivecoating allows bonding and lamination at much lower temperatures andpressures. The B-staged TPI coating flows easily and bonds quickly androbustly at moderate conditions, similar to what might be used forconventional thermoset adhesive coatings.

The under curing of the B-stage can involve both leaving solvent in thelayer and a low conversion of the polyamic-acid polymer (PAA) topolyimide polymer (PI). Traditionally, TPI adhesive coatings have allsolvent removed and have near full-conversion to PI before thelamination process.

The reduction in lamination temperature and pressure dramaticallyreduces the equipment required and imparts much less stress on thelamination, both in processing and in the final interlayers. In fact,robust TPI bondlines can be created between surfaces held together withbinder clips and baking the assembly in a toaster oven.

During the B-staged TPI bonding process at moderate temperature, theresidual organic solvent (NMP preferred) escapes cleanly, withoutblistering. Microchannels form within the bondline to facilitate thesolvent outgassing. These same bondline microchannels also facilitatethe moisture outgassing from the polymer's condensation reaction, as thePAA converts to PI. The bondline microchannels tend to collapse afterthe required outgassing, and do not appreciably impact the bond strengthor thermal impedance of the bondline. Bondline microchannels can beeliminated by applying high pressure for a short period of time afterthe outgassing process has been completed.

Residual solvent in the B -staged TPI layer can providesurface-cleaning, facilitating a robust bond, during the heating-up ofthe lamination process.

Overwrought fears of NMP exposure have contributed to the traditionalprocessing of TPI, where the TPI polymer is brought to or near itsfully-cured state, eliminating the opportunity to utilize the uniqueproperties of a truly B-staged TPI coating. This scare campaign aboutNMP was orchestrated ironically by manufacturers of fluorocarboncleaning solutions, which competed with the supposedly hazardous NMPsolvent in electronic processes. Years later, these fluorocarbons werebanned, due to conclusive evidence of damaging the atmosphere's ozonelayer. According their MSDSs, NMP is actually safer than rubbingalcohol, unless the exposed is pregnant or a flathead minnow. NMP is acommon active-ingredient in paint remover.

TPI bondlines utilize the hydroxyl groups of the PAA polymer tofacilitate bonding, resulting in a robust permanent bond well beforefull curing.

After the initial bonding process, further curing of the TPI, convertingPAA to PI, can be done through simple post-baking or even utilizing thehigh temperature exposure in downstream processes, such as reflowsoldering, and even in use.

The B-staged TPI technology can utilize a wide range of substrates suchas film, foil, fabric, and release liner.

The B-staged TPI technology can be applied in a wide range ofthicknesses (dry, 0.1-2 mil or 2-50 micron), on one or both sides of asubstrate. Even thicker coatings would be possible, by nip-laminatingTPI sheet-adhesive to a TPI-coated substrate. Optimal coating thicknesswould be determined by the smoothness of the surfaces to be bonded, andwhether encapsulation is required of certain features.

The B-stage TPI technology can provide robust bonding for a wide rangeof surfaces: metal, glass, ceramic, semiconductor, and plastic.

A TPI bondline can provide robust adhesion over a wide range ofconditions, even when being extremely thin (down to 0.08-0.12 mil, or2-3 um). This is critical in reducing both cost as TPI polymers can berelatively costly, especially compared to conventional thermosetadhesives and thermal impedance of the bondline.

A TPI bondline is structurally and electrically durable from cryogenicto 300° C., under severe interlaminar shear stress, due to CTE mismatch,under vibration and shock, under extreme radiation-exposure, and inpractically all chemical environments. TPI polymer is also naturallyflame-retardant.

TPI polymer accepts high loading of inert fillers extremely well, as thecollapsing layer of the PAA with drying and curing to PI ensuresexcellent mating of polymer and particles.

The curing of the TPI polymer at moderate temperatures can be assistedwith the aid of catalysts.

B-staged TPI coatings can be dry to the touch at room temperature, evenwhen they contain relatively high levels of residual solvent. Thisfacilitates both packaging and handling.

B-staged TPI coatings have an indefinite shelf life at room temperature.

The B-staged TPI technology will also be effective for a robust coverlayer for demanding electronic and electrical applications.Additionally, the B-staged TPI technology will be effective for a robustprimary insulation for demanding wiring and magnet applications.

There are many potential applications that could use this B-staged TPItechnology for robust interface-bonding and cover layer/primaryinsulation in electronics and elsewhere. These include otherapplications where generated heat must be dissipated (such asheat-sink/baseplate attachment, electronic controls, light-emittingdiodes, thermoelectric coolers); where high-temperature-resistance iscritical (bus bars, resistive-heaters, wind-turbine generators); whereradiation-resistance and cryogenic-resistance is critical(superconducting and other high-field magnets: particle accelerators,fusion reactors, MRI); and where naturally flame-retardant,non-halogenated insulation is critical (aerospace, subway motors).

Under or partially cured TPI film and coating will have much more flowto fill in the micro-irregularities in the adjacent surface of thelaminate, ensuring surface intimacy and have much greater reactivity forsurface adhesion than a fully-cured TPI coating. This is why lesstemperature, pressure and dwell time are required for the lamination ofa partially cured TPI coating. This is especially important when a TPIcoating of only a few microns, for example, 3 microns or 0.00012″, isused to laminate surfaces together. The standard thickness of a TPIcoating in the industry is 2-5 micron. Polyimide adhesives are veryrugged when properly laminated, even with the bonding of dissimilarmaterials, and therefore don't need much thickness between the layers.In comparison, a conventional thermoset adhesive bondline may require25-50 micron thickness or more for the same applications.

Traditional fully cured TPI coating needs a significant amount ofpressure to ensure a good bond, generally at temperatures well above300° C. and with dwell times in excess of 60 minutes, as the polymer isvery resistance to deformation and moves very slowly into the adjacentsurface. This slow/no movement of polymer can become a significantproblem during lamination when the lamination equipment and fixturingdoes not have very consistent applied pressure.

The water vapor evolved during the curing of the TPI polymer during thelamination process at high temperature and low pressure needs to beevacuated from the bondline between the adjacent surfaces, or elsesevere blistering will occur, which destroys the lamination. Water vaporpressure at elevated temperatures will force the evolved water to escapea laminate bondline held under considerably lower pressure than theinherent water vapor during the heating process. For instance, aB-staged TPI bondline that reaches 250° C. during the lamination processwill be evolving water that has a vapor pressure of about 500 psi and ifthe applied pressure on the lamination is, for example 5-50 psi, thewater vapor can escape easily.

Under low applied-pressure during lamination, the water evolved from thecondensation reaction, or conversion, of the polyamic-acid polymer topolyimide polymer escapes the lamination bondline in microchannels inthe TPI coating interface. As the laminate is cooled, the microchannelscollapse, allowing the TPI coating to form a robust bondline between theadjacent surfaces.

After complete outgassing of the TPI bondline at the maximumtemperature, much higher pressure can be applied to the bondline(100-1000 psi) in the lamination process. This ensures that the bondlineintegrity, including complete conformance of the laminate materials, islocked-in. This high final pressure as described above effectivelyeliminates the bondline's ability to re-form microchannels for watervapor outgassing without blistering.

If the TPI laminate has not seen a high pressure lamination step, thenthe microchannels can re-form if or when the laminate sees a temperatureabove the highest it has already experienced, and the additional evolvedwater vapor can escape. For instance, a TPI laminate made at 230° C.under low pressure can survive a downstream soldering process at 260°C., as the evolved water vapor from the TPI's condensation reaction atthe even-higher temperature can escape thru the micro-channels withoutblistering.

These, and other features and advantages of the invention will becomemore evident from the description of the preferred embodimentaccompanied by the drawings which follows.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing of the chemical process of the invention;

FIG. 2 is a table comparing the invention with the prior art;

FIG. 3 is a table describing the invention in terms of the physical andchemical parameters of the succeeding stages of the TPI coating; and

FIG. 4 is a schematic drawing of the apparatus suitable for carrying outthe process of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The preferred embodiment of the invention is a Thermoplastic Polyimide(TPI) polymer adhesive coated laminating film in which the TPI coatingis under cured or B-staged as described above. The coating may be placedon one side or both. The substrate may comprise any suitable polyimidematerial such as DuPont Kapton FPC or CR-ST films or Kaneka Apical AVfilm of a thickness in the 0.5-5 mil range. Other substrates andthicknesses that are suitable are copper foils in the 0.7-5 mil rangeand glass fabrics in the 2-10 mil range. Coating formulations that haveproved successful are FM901 from Fraivillig Technologies Boston, Mass.and LARC-TPI from Imitech Corporation, Schenectady, N.Y.

FIG. 3 is a table which describes the invention through the physical andchemical parameters in the different steps of the processes offabricating and using the invention, i.e., formulation of thepolyamic-acid polymer in solution, coating and B-staged curing of theTPI polymer, and post-lamination use in suitable applications. Thesepercentages are only of the TPI coating, and do not include anysubstrate material. As will be seen in FIGS. 2 and 3, the partial, undercure, or B-staged state of the resulting product is produced at a lowertemperature than prior art or traditional cures and results in a muchlower TPI content and much higher residual solvent content than thepresently available fully cured TPI films.

An example of a process for preparing the films with reference to FIG. 4is as follows: The adhesive is agitated at all times in holding tank 48and circulated through a coating bath 46. To optimize the ‘wetting’ ofthe adhesive to the Kapton film, the film is corona-treated, both by themanufacturer (DuPont) and immediately before coating at a contact coatersuch as Lamart Corporation, Clifton, N.J.

A gravure roll coating head 52, which lays down a specific amount of wetadhesive based on its cell size, rotates through bath 46. The gravurecells pick up the adhesive in the coating bath and deposit the adhesiveonto the film upon contact with back-up roll 54. The gravure roll laysdown about 20 microns of wet polymer, consisting of about 15% polymerand 85% solvent, onto the film.

The coated film web is then transported through the oven 56, where thesolvent is evaporated and the adhesive polymer is cured. The heatingportion, utilizing impinged hot air, of the single zone coating oven isabout 20 feet long and the line-speed is 45-50 feet/minute, resulting ina very short dwell time of 24-27 seconds. Upon emerging from the oven,the TPI coated film is now wound up on a roll, and will have an infiniteshelf life, assuming standard storage conditions. The film is coated oneside at a time. If a two-side coating is required, the film is merelysent through for a second pass.

During lamination processing, when the TPI bond film reaches atemperature in excess of that during the above coating and drying, theadhesive will activate outgassing the remaining solvent and beginconverting to polyimide.

The polyamic-acid polymer is synthesized in a solution of a polarsolvent (such as NMP or DMAC), and is applied to the film surface by,for example, the coating technique described above. The TPI precursor,polyamic-acid polymer, is synthesized by the reaction of diamine anddianhydride monomers, in approximately 50:50 molar concentrations. Inthese TPI syntheses, the diamine monomer is dissolved into the polarsolvent, and then the dianhydride monomer is added slowly to build theTPI polymer chain.

Typical TPI diamine can be one or more of the following monomers: DABA,3,3′-DABP, 3,4′-DABP, RDEDA, TPER, 3,4′-ODA, 4,4′-ODA, 4,4′-MDA, analiphatic diamine, or a silicon-diamine among others. Typical TPIdianhydride can be one or more of the following monomers: APD, BPDA,BTDA, ODPA, PMDA, or 6FDA among others. TPI-precursor solutions,polyamic-acid polymer in solution, are also available commercially, suchas LARC-TPI or Fraivillig Technologies FM901 solutions.

The choice of monomers in the TPI polymer determines its thermalprocessing requirements and thermal resistance, which are related.Typically, the higher the thermal resistance of the polymer, the higherthe required process temperatures to cure the polymer. Both the thermalprocessing requirements and the inherent thermal resistance of a TPIpolymer are typically correlated to the material's glass-transitiontemperature (Tg). In most Commercial applications lower Tg TPI polymersare preferable, as 1) most electronic applications do not requirethermal resistances exceeding 250° C. for a significant amount of timeand 2) lower Tg material can be processed and cured at much lowertemperature, which minimizes the amount of special processing, stress,and degradation applied to other materials in the construction. The sameprinciples taught in this invention can also be applied to higher Tg TPIpolymers. The biggest difference would be in the required processingtemperatures.

As variations in the above-described preferred embodiment may be madewithin the general concept of the disclosure, the invention isaccordingly defined by the following claims.

What is claimed is:
 1. A heat activated thermoplastic laminating filmfor joining two surfaces comprising in combination: A. a substrate; andB. a heat activated thermoplastic adhesive coated on said substrate,said adhesive comprising in combination: i. a solvent; and ii. a mixtureof polyamic-acid polymer and thermoplastic polyimide polymer solidsdisposed in said solvent, said mixture containing no greater than 50%thermoplastic polyimide of the total polymer mass and said mixturefurther containing an amount of solvent of between 20 and 60% of thetotal mass of the mixture.
 2. The laminating film of claim 1 whereinsaid solvent is selected from the group consisting of NMP and DMAC. 3.The laminating film of claim 1 wherein said polyamic-acid polymercomprises a mixture of diamine and dianhydride monomers, said diaminemonomer is selected from the group consisting of DABA, 3,3′-DABP,3,4′-DABP, RDEDA, TPER, 3,4′-ODA, 4,4′-ODA, 4,4′-MDA, an aliphaticdiamine, and a silicon-diamine; and said dianhydride monomer is selectedfrom the group consisting of APD, BPDA, BTDA, ODPA, PMDA, and 6FDA. 4.The process of fabricating a heat activated thermoplastic laminatingfilm for joining two surfaces comprising in combination the steps of: A.providing a substrate; B. providing a solvent; C. providing a quantityof polyamic-acid polymer diamine and dianhydride constituent monomers;D. adding said monomers to said solvent to create a polyamic-acidsolution coating bath; E. providing a gravure coating roller arranged torotate through said bath and hold a quantity of said polyamic-acidsolution on its surface; F. passing said substrate in contact with saidsurface to deposit a coating of said polyamic-acid solution on saidsubstrate; G. providing an oven; H. passing said coated substratethrough said oven at a temperature of between 85 and 190° C., saidcoating upon emerging from said oven comprising a mixture ofpolyamic-acid polymer and thermoplastic polyimide polymer solidsdisposed in said solvent, said mixture containing no greater than 50%thermoplastic polyimide of the total polymer mass and said mixturefurther containing an amount of solvent of between 20 and 60% of thetotal mass of the mixture.
 5. The process of claim 4 wherein saidsolvent is selected from the group consisting of NMP and DMAC.
 6. Theprocess of claim 4 wherein said polyamic-acid polymer comprises amixture of diamine and dianhydride monomers, said diamine monomer isselected from the group consisting of DABA, 3,3′-DABP, 3,4′-DABP, RDEDA,TPER, 3,4′-ODA, 4,4′-ODA, 4,4′-MDA, an aliphatic diamine, and asilicon-diamine; and said dianhydride monomer is selected from the groupconsisting of APD, BPDA, BTDA, ODPA, PMDA, and 6FDA.